US4384081A - Process for production of hydrogenated conjugated diene polymers - Google Patents

Process for production of hydrogenated conjugated diene polymers Download PDF

Info

Publication number
US4384081A
US4384081A US06/342,591 US34259182A US4384081A US 4384081 A US4384081 A US 4384081A US 34259182 A US34259182 A US 34259182A US 4384081 A US4384081 A US 4384081A
Authority
US
United States
Prior art keywords
catalyst
polymer
carbon
hydrogenated
conjugated diene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/342,591
Other languages
English (en)
Inventor
Yoichiro Kubo
Tetsu Ohishi
Kiyomori Ohura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Nippon Zeon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co Ltd filed Critical Nippon Zeon Co Ltd
Application granted granted Critical
Publication of US4384081A publication Critical patent/US4384081A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation

Definitions

  • This invention relates to an improvement in a process for producing a hydrogenated conjugated diene polymer. More specifically, it relates to a process for producing a hydrogenated conjugated diene polymer, which comprises hydrogenating the carbon-carbon double bonds of a conjugated diene polymer in solution using a hydrogenating catalyst supported on a carrier, and after the hydrogenation reaction, separating and recovering the hydrogenated conjugated diene polymer from the hydrogenated conjugated diene polymer solution without separating the supported catalyst therefrom.
  • a supported catalyst composed of a hydrogenating catalyst comprising a metallic element or non-metallic element supported on a carrier such as activated carbon in the suspended state in a solution, remove the used catalyst from the hydrogenated polymer solution by a suitable treating means after the hydrogenating reaction has been completed, and thereafter separate and recover the hydrogenated polymer.
  • the removal of the catalyst from the solution is for the purpose not only recovering the catalyst for reuse, but also preventing a certain kind of catalyst element remaining in the hydrogenated polymer from exerting adverse effects, such as degradation, on the polymer.
  • the carrier used is generally of a large particle diameter in order to facilitate separation of the catalyst. Since, however, a carrier of a large particle diameter, if it remains in the hydrogenated polymer, would markedly reduce the strength characteristics of a vulcanized product of the polymer, the carrier should be separated together with the catalyst.
  • Separation of the supported catalyst from the reaction mixture is effected frequently by a filtration method using various filters or a centrifugal separating method.
  • the reaction system In contrast to the hydrogenation of a low-molecular-weight compound, in the case of hydrogenation of a polymer, the reaction system has a high viscosity. Accordingly, it is very difficult to separate the supported catalyst from such a reaction system. Separation will become easy if the viscosity of the reaction system is decreased by adding a large amount of a solvent, or using a filtration aid. This, however, gives rise to new problems. For example, a great deal of heat energy is consumed for recovery and regeneration of the solvent. Or the separation of the filtration aid from the catalyst is not easy.
  • this object is achieved by a process for producing a hydrogenated conjugated diene polymer, which comprises hydrogenating the carbon-carbon double bonds of a conjugated diene polymer in solution using a supported catalyst composed of a hydrogenating catalyst supported on a specified carbon carrier, and after the hydrogenation reaction has been completed, separating and recovering the conjugated diene polymer without separating the catalyst from the hydrogenated polymer solution.
  • the solvent can be easily recovered and regenerated.
  • the supported catalyst does not have to be separated, it is not necessary to use a filtration aid, etc.
  • various devices for separation of the supported catalyst such as a decanter, a centrifugal separator and a filter are not at all required. This is economically advantageous in that the hydrogenating process can be very much simplified.
  • the particle diameter of carbon used as a carrier is not restricted, and it is only necessary to consider its allowable maximum particle diameter.
  • the hydrogenation reaction can be performed by using a highly active catalyst supported on carbon having the smallest possible particle diameter.
  • the carbon carrier used in this invention has an average particle diameter of 5 m ⁇ to 10 ⁇ , preferably 20 m ⁇ to 10 ⁇ and a specific surface area of 5 to 2000 m 2 /g, preferably 20 to 1500 m 2 /g, in view of the activity of the supported catalyst and of the fact that the catalyst is allowed to remain in the resulting hydrogenated polymer.
  • carbon black used for coloration, or as a reinforcing agent for rubber or as an electrically conductive filler, that is, carbon black produced from petroleum-type or coal-type heavy oils, natural gases, etc. as raw materials by the furnace process or channel process.
  • Specific examples of the carbon black are FF, HMF, SRF, etc. produced by the gas furnace process, SAF, HAF, ISAF, FEF, CF, etc. produced by the oil furnace process; and coloring HCC, MCC, etc. and EPC, MPC, etc. for rubber which are produced by the channel process.
  • a suitable carbon may be selected by considering the catalytic activity and effects on the properties of a vulcanized product of the hydrogenated polymer. SRF, FEF or CF type carbon blacks are preferred, and CF-type carbon black having a specific surface area of more than 700 m 2 /g is most preferred.
  • the hydrogenating catalyst used in this invention may be any hydrogenating catalyst which is a metal element catalyst or non-metal element catalyst having hydrogenating activity and does not adversely affect the resulting polymer even if it remains there after the polymerization.
  • it may comprise at least one element selected from the group consisting of Ru, Rh, Pd, Ir, Os, Pt, Ag and Au.
  • a catalyst composed of both Pd and at least one element selected from the group consisting of elements of Groups Ia, IIa, IIIa, IIIb, IVa, IVb, Va, VIa and VIIa, Ag, Au, Sb and Te is especially preferred because it has high activity and a high hydrogenating efficiency, and it does not adversely affect the hydrogenated polymer even when it remains there.
  • the metal element or non-metal element may be supported on the carbon carrier by any conventional method for preparing supported catalysts.
  • the aforesaid metal element or non-metal element is directly supported on the carbon carrier.
  • an aqueous solution of a salt of such an element is impregnated in the carbon carrier, followed by reduction to provide a carbon-supported catalyst.
  • the amount of the catalyst element supported on the carbon carrier is 0.001 to 30% by weight, preferably 0.01 to 10% by weight, based on the carrier.
  • the amount of the carrier-supported catalyst used may be properly determined according to the type of the polymer to be hydrogenated, and the desired degree of hydrogenation. If it is too large, adverse effects are exerted on the properties of vulcanized products of the resulting polymer. Hence, it is usually not more than 2000 ppm, preferably not more than 1000 ppm, as the amount of the element supported.
  • the conjugated diene polymer used in this invention is prepared by polymerizing 10 to 100% by weight of a conjugated diene monomer and 90 to 0% by weight of an ethylenically unsaturated monomer by solution polymerization, emulsion polymerization, etc.
  • Examples of the conjugated diene monomer are 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, and 1,3-pentadiene.
  • ethylenically unsaturated monomer examples include unsaturated nitriles such as acrylonitrile and methacrylonitrile; monovinylidene aromatic hydrocarbons such as styrene and alkylstyrenes (e.g., o-, m- and p-methylstyrene and ethylstyrene); unsaturated carboxylic acids and the esters thereof such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate; vinyl pyridine; and vinyl esters such as vinyl acetate.
  • unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • monovinylidene aromatic hydrocarbons such as styrene and alkylstyrenes (e.g
  • Typical examples of the conjugated diene polymer are polybutadiene, polyisoprene, a butadiene/styrene random or block copolymer, and an acrylonitrile/butadiene random or block copolymer.
  • the resulting polymer solution is directly hydrogenated.
  • the polymer is a solid, it is dissolved in a solvent and hydrogenated in solution.
  • the concentration of the polymer solution is 1 to 70% by weight, preferably 1 to 40% by weight.
  • Any solvent may be used which does not adversely affect the catalyst and can dissolve the polymer to be hydrogenated. Examples include benzene, toluene, xylene, hexane, cyclohexane, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, and cyclohexane.
  • the reaction temperature is 0° to 300° C., preferably 20° to 150° C. At a reaction temperature of more than 150° C., side-reactions tend to take place, and this is undesirable for selective hydrogenation.
  • the solvent may undergo hydrogenation, or the ethylenically unsaturated monomer unit other than the conjugated diene unit of the polymer, for example, the nitrile group of acrylonitrile or the benzene ring of styrene, may undergo hydrogenation.
  • the pressure of hydrogen is a from atmospheric pressure to 300 kg/cm 2 , preferably 5 to 200 kg/cm 2 . Pressures higher than 300 kg/cm 2 may be used, but are not feasible in commercial practice because the cost of equipment increases and the handling of the apparatuses is troublesome.
  • the hydrogenated polymer is separated from the polymer solution containing the carrier-supported catalyst by any method which is usually employed in recovering a polymer from a polymer solution.
  • the separation can be effected by a steam coagulation method which involves directly contacting the polymer solution with steam, a drum drying method which comprises dropping the polymer solution onto a heated rotating drum and allowing the solvent to evaporate off, and a method which comprises adding a non-solvent to the polymer solution of precipitate the polymer.
  • the hydrogenated polymer containing the supported catalyst can be separated from the solution by using such a separating method.
  • the separated polymer is subjected to a water-removing step and a drying step by, for example, hot air drying, vacuum drying or extrusion drying to recover the hydrogenated polymer as a solid.
  • the hydrogenated conjugated polymer obtained by the process of this invention and containing the carrier-supported catalyst is the same in properties from a hydrogenated conjugated diene polymer not containing the catalyst, and can be used in a wide range of applications because of its excellent weatherability, ozone resistance, thermal stability and cold climate resistance.
  • the average particle diameter of carbon black was determined from a particle diameter distribution curve which was obtained by measuring the particle diameter by an electron microphotograph.
  • the specific surface area of the carbon black is calculated by the BET method from the amount of nitrogen absorbed which was measured by the low temperature nitrogen adsorption method.
  • the degree of hydrogenation of the carbon-carbon double bonds was measured by the iodine value method.
  • carrier-supported catalysts were each prepared by dipping carbon black or activated carbon in an aqueous solution of PdCl 2 or RhCl 3 and reducing the Pd or Rh salt with formaldehyde/sodium hydroxide in accordance with an ordinary method for preparing an activated carbon-supported catalyst.
  • the inside of the autoclave was purged with nitrogen, and the copolymer was hydrogenated at 60° C. for 4 hours while passing hydrogen under a pressure of 20 kg/cm 2 .
  • the degree of hydrogenation of the double bonds was 83.0%.
  • reaction product polymer solution
  • steam was blown into it to obtain crumbs which were then vacuum-dried (sample No. 1).
  • the remainder of the reaction mixture was diluted with a large amount of acetone, and the catalyst was separated from it by a centrifugal separator. Steam was then blown into the residue to obtain crumbs which were then vacuum-dried (sample No. 2).
  • Each of the two hydrogenated polymer samples was compounded on a roll in accordance with the compounding recipe shown in Table 4, and the compound was heated under pressure at 155° C. for 20 minutes to form a vulcanized product.
  • the properties of the vulcanized product were measured in accordance with JIS K-6301.
  • sample No. 3 A part of the product was coagulated, without separating the catalyst from it, by blowing steam into it, and dried (sample No. 3). The remainder of the product was coagulated and dried after separating the catalyst (sample No. 4) as in the preparation of sample No. 2.
  • Example No. 5 A part of the reaction product, without separating the catalyst from it, was coagulated by blowing steam into it and dried (sample No. 5). The remainder of the product was coagulated by blowing steam into it after separating the catalyst from it, and dried (sample No. 6) in the same way as in the preparation of sample No. 2.
  • the two hydrogenated polymer samples were compounded in accordance with the same compounding recipe as in Table 4 and vulcanized under the same conditions as shown in Example 1.
  • the degree of hydrogenation of the double bonds was 78.7%.
  • Example No. 8 The remainder of the product was coagulated by blowing steam into it after separating the catalyst from it, and dried (sample No. 8) in the same way as in Example 1.
  • the two hydrogenated polymer samples were each compounded in accordance with the same compounding recipe as shown in Table 4 and vulcanized under the same conditions as in Example 1.
  • the hydrogenated styrene-butadiene copolymer prepared in Referential Example 2 was recovered in the same way as in Example 1 as a polymer containing the carrier supported catalyst (sample No. 11) and a polymer free from the catalyst (sample No. 12).
  • the two hydrogenated polymer samples were each mixed with compounding agents shown in Table 6 to obtain a rubber compound.
  • the rubber compound was heated under pressure at 145° C. for 45 minutes to obtain a vulcanized product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US06/342,591 1979-12-08 1982-01-25 Process for production of hydrogenated conjugated diene polymers Expired - Lifetime US4384081A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP15935879A JPS5682803A (en) 1979-12-08 1979-12-08 Preparation of hydrogenated conjugated polymer
JP54-159358 1979-12-08

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06213369 Continuation 1980-12-05

Publications (1)

Publication Number Publication Date
US4384081A true US4384081A (en) 1983-05-17

Family

ID=15692093

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/342,591 Expired - Lifetime US4384081A (en) 1979-12-08 1982-01-25 Process for production of hydrogenated conjugated diene polymers

Country Status (4)

Country Link
US (1) US4384081A (enrdf_load_stackoverflow)
JP (1) JPS5682803A (enrdf_load_stackoverflow)
CA (1) CA1172799A (enrdf_load_stackoverflow)
DE (1) DE3046251C2 (enrdf_load_stackoverflow)

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4452951A (en) * 1981-07-24 1984-06-05 Nippon Zeon Co. Ltd. Process for hydrogenating conjugated diene polymers
US4486480A (en) * 1981-12-30 1984-12-04 Toyoda Gosei Co., Ltd. Rubber hose comprising a liquid nitrile-butadiene copolymer incorporated into a partially hydrogenated unsaturated acrylonitrile-butadiene copolymer
US4559390A (en) * 1982-05-18 1985-12-17 Nippon Zeon Co., Ltd. Method for preventing degradation and deterioration of vulcanized rubber material
US4656219A (en) * 1982-03-27 1987-04-07 Nippon Zeon Co., Ltd. Rubber member having oil resistance and resistance to deterioration
US4843114A (en) * 1988-01-29 1989-06-27 The United States Of America As Represented By The Secretary Of The Army Rubber compound for tracked vehicle track pads
US4910267A (en) * 1981-12-28 1990-03-20 Nippon Zeon Co., Ltd. Oil-resistant and anti-degrading rubber article
US4914160A (en) * 1988-06-23 1990-04-03 Hormoz Azizian Deuteration of unsaturated polymers and copolymers
US4925900A (en) * 1988-09-16 1990-05-15 Polysar Limited Halogenated-hydrogenated acrylonitrile-butadiene rubber
US4965323A (en) * 1983-05-17 1990-10-23 Nippon Zeon Co., Ltd. Method of vulcanizing rubber at pH 5 to 10
US5075388A (en) * 1990-12-13 1991-12-24 Rempel Garry L Amine modified hydrogenation of nitrile rubber
US5107051A (en) * 1989-03-14 1992-04-21 Exxon Chemical Patents Inc. Halogen resistant hydrotreating process and catalyst
US5208296A (en) * 1992-09-02 1993-05-04 Polysar Rubber Corporation Nitrile rubber hydrogenation
US5210151A (en) * 1992-09-02 1993-05-11 Polysar Rubber Corporation Hydrogenation of nitrile rubber
US5241013A (en) * 1992-09-02 1993-08-31 Polysar Rubber Corporation Catalytic hydrogenation of nitrile rubber
US5258467A (en) * 1992-09-02 1993-11-02 Polysar Rubber Corporation Catalytic solution hydrogenation of nitrile rubber
US5314741A (en) * 1992-10-07 1994-05-24 The Goodyear Tire & Rubber Company Rubber article having protective coating
US5565092A (en) * 1994-03-16 1996-10-15 Exxon Chemical Patents Inc. Halogen resistant hydrogenation process and catalyst
US6403722B1 (en) 2000-10-03 2002-06-11 The University Of Akron Dynamically vulcanized elastomeric blends including hydrogenated acrylonitrile-butadiene copolymers
US6538071B1 (en) 1999-09-07 2003-03-25 Bayer Aktiengesellschaft Rubber mixtures for roller coatings
US6573333B2 (en) 2000-08-22 2003-06-03 Bayer Aktiengesellschaft Mixtures of olefin polymers and nitrile rubbers
CN1118485C (zh) * 1997-12-19 2003-08-20 国际壳牌研究有限公司 氢化大分子有机底物的方法
US20030181604A1 (en) * 2002-01-23 2003-09-25 Roland Parg Nitrile rubber mixtures with a low tendency towards mold contamination
US20040018312A1 (en) * 2002-07-25 2004-01-29 Lord Corporation Ambient cured coatings and coated rubber products therefrom
US7037982B2 (en) 2001-01-17 2006-05-02 Bayer Aktiengesellschaft Rubber mixtures for roll coverings
US20090011163A1 (en) * 2006-03-09 2009-01-08 Manoj Ajbani Compatibalized Blends of Polyphenylene Sulfide and Thermoplastic Vulcanizate
US20090015933A1 (en) * 1999-07-31 2009-01-15 Ho Young Choi Projection lens system
US20090061134A1 (en) * 2006-03-09 2009-03-05 Manoj Ajbani Flexible, hydrocarbon-resistant polyarylenesulfide compounds and articles
US7737225B1 (en) 2005-02-18 2010-06-15 The United States Of America As Represented By The Secretary Of The Army High performance elastomeric compound
US9182056B2 (en) 2012-04-13 2015-11-10 Ticona Llc Pipe section having polyarylene sulfide composition barrier layer
US9493646B2 (en) 2012-04-13 2016-11-15 Ticona Llc Blow molded thermoplastic composition
US9494262B2 (en) 2012-04-13 2016-11-15 Ticona Llc Automotive fuel lines including a polyarylene sulfide
US9718225B2 (en) 2013-08-27 2017-08-01 Ticona Llc Heat resistant toughened thermoplastic composition for injection molding
US9758674B2 (en) 2012-04-13 2017-09-12 Ticona Llc Polyarylene sulfide for oil and gas flowlines
US9757892B2 (en) 2013-08-27 2017-09-12 Ticona Llc Thermoplastic composition with low hydrocarbon uptake
US9765219B2 (en) 2012-04-13 2017-09-19 Ticona Llc Polyarylene sulfide components for heavy duty trucks
US10494467B2 (en) 2013-10-30 2019-12-03 Arlanxeo Deutschland Gmbh Copolymer rubber containing nitrile groups
US10544234B2 (en) 2013-10-30 2020-01-28 Arlanxeo Deutschland Gmbh Functionalized copolymer rubber containing nitrile groups
US11046799B2 (en) 2016-01-25 2021-06-29 Arlanxeo Deutschland Gmbh Hydrogenated nitrile-butadiene-PEG-acrylate co-polymers
US11286325B2 (en) 2017-12-21 2022-03-29 Arlanxeo Deutschland Gmbh Nitrile-diene-carboxylic acid ester copolymers
WO2022064031A1 (en) * 2020-09-28 2022-03-31 Arlanxeo Deutschland Gmbh Partially hydrogenated diene polymers
US11827726B2 (en) 2018-12-17 2023-11-28 Arlanxeo Deutschland Gmbh Process for producing PEG acrylate-HNBR copolymer
US12104058B2 (en) 2014-12-11 2024-10-01 Ticona Llc Stabilized flexible thermoplastic composition and products formed therefrom

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1241189B1 (en) * 2001-03-14 2006-08-16 Kuraray Co., Ltd. Process for producing a hydrogenated polymer
CA2487744A1 (en) 2004-11-18 2006-05-18 Lanxess Inc. Peroxide curable rubber composition comprising hnbr
CN101903243B (zh) 2007-10-19 2014-12-10 洛德公司 用于飞行器辅助动力单元的具有弹性体构件的悬架系统
DE102009038615A1 (de) 2009-08-26 2011-03-10 Lanxess Deutschland Gmbh Vulkanisierbare Mischungen und deren Verwendung für die Reparatur von kautschukbasierten Formkörpern
EP3330294B1 (en) 2016-12-05 2020-08-26 Dayco Europe S.R.L. Power transmission belt
EP3333196B1 (de) 2016-12-09 2020-05-13 ARLANXEO Deutschland GmbH Hydrierte nitril-dien-carbonsäureester-copolymere
EP3387931B1 (de) 2017-04-10 2020-07-15 ARLANXEO Deutschland GmbH Vulkanisierbare zusammensetzung enthaltend hxnbr-latex und polyfunktionales epoxid
US20200140595A1 (en) 2017-07-25 2020-05-07 Arlanxeo Deutschland Gmbh Vulcanizable Compositions Comprising Hydrogenated Nitrile-Diene-Carboxylic Ester Copolymer and Silica

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598886A (en) * 1965-09-15 1971-08-10 Borg Warner Hydrogenated block copolymers
US4337329A (en) * 1979-12-06 1982-06-29 Nippon Zeon Co., Ltd. Process for hydrogenation of conjugated diene polymers
GB2011911B (en) 1977-10-20 1982-09-15 Johnson Matthey Co Ltd Production of stable polymers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2842504A (en) * 1954-08-23 1958-07-08 Phillips Petroleum Co Hydrogenation catalyst
US3700637A (en) * 1970-05-08 1972-10-24 Shell Oil Co Diene-nitrile rubbers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598886A (en) * 1965-09-15 1971-08-10 Borg Warner Hydrogenated block copolymers
GB2011911B (en) 1977-10-20 1982-09-15 Johnson Matthey Co Ltd Production of stable polymers
US4337329A (en) * 1979-12-06 1982-06-29 Nippon Zeon Co., Ltd. Process for hydrogenation of conjugated diene polymers

Cited By (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4452951A (en) * 1981-07-24 1984-06-05 Nippon Zeon Co. Ltd. Process for hydrogenating conjugated diene polymers
US4910267A (en) * 1981-12-28 1990-03-20 Nippon Zeon Co., Ltd. Oil-resistant and anti-degrading rubber article
US4486480A (en) * 1981-12-30 1984-12-04 Toyoda Gosei Co., Ltd. Rubber hose comprising a liquid nitrile-butadiene copolymer incorporated into a partially hydrogenated unsaturated acrylonitrile-butadiene copolymer
US4656219A (en) * 1982-03-27 1987-04-07 Nippon Zeon Co., Ltd. Rubber member having oil resistance and resistance to deterioration
US4559390A (en) * 1982-05-18 1985-12-17 Nippon Zeon Co., Ltd. Method for preventing degradation and deterioration of vulcanized rubber material
US4965323A (en) * 1983-05-17 1990-10-23 Nippon Zeon Co., Ltd. Method of vulcanizing rubber at pH 5 to 10
US4843114A (en) * 1988-01-29 1989-06-27 The United States Of America As Represented By The Secretary Of The Army Rubber compound for tracked vehicle track pads
WO1989007121A1 (en) * 1988-01-29 1989-08-10 United States Of America, Represented By The Secre Improved rubber compound for tracked vehicle track pads
US4914160A (en) * 1988-06-23 1990-04-03 Hormoz Azizian Deuteration of unsaturated polymers and copolymers
US4925900A (en) * 1988-09-16 1990-05-15 Polysar Limited Halogenated-hydrogenated acrylonitrile-butadiene rubber
US5107051A (en) * 1989-03-14 1992-04-21 Exxon Chemical Patents Inc. Halogen resistant hydrotreating process and catalyst
US5075388A (en) * 1990-12-13 1991-12-24 Rempel Garry L Amine modified hydrogenation of nitrile rubber
US5241013A (en) * 1992-09-02 1993-08-31 Polysar Rubber Corporation Catalytic hydrogenation of nitrile rubber
US5210151A (en) * 1992-09-02 1993-05-11 Polysar Rubber Corporation Hydrogenation of nitrile rubber
US5208296A (en) * 1992-09-02 1993-05-04 Polysar Rubber Corporation Nitrile rubber hydrogenation
US5258467A (en) * 1992-09-02 1993-11-02 Polysar Rubber Corporation Catalytic solution hydrogenation of nitrile rubber
US5314741A (en) * 1992-10-07 1994-05-24 The Goodyear Tire & Rubber Company Rubber article having protective coating
US5565092A (en) * 1994-03-16 1996-10-15 Exxon Chemical Patents Inc. Halogen resistant hydrogenation process and catalyst
CN1118485C (zh) * 1997-12-19 2003-08-20 国际壳牌研究有限公司 氢化大分子有机底物的方法
US20090015933A1 (en) * 1999-07-31 2009-01-15 Ho Young Choi Projection lens system
US6538071B1 (en) 1999-09-07 2003-03-25 Bayer Aktiengesellschaft Rubber mixtures for roller coatings
US20030139493A1 (en) * 1999-09-07 2003-07-24 Erich Fuchs Rubber mixtures for roller coatings
US6573333B2 (en) 2000-08-22 2003-06-03 Bayer Aktiengesellschaft Mixtures of olefin polymers and nitrile rubbers
US20040014892A1 (en) * 2000-08-22 2004-01-22 Hans Magg Mixtures of olefin polymers and nitrile rubbers
US6765064B2 (en) 2000-08-22 2004-07-20 Bayer Aktiengesellschaft Mixtures of olefin polymers and nitrile rubbers
US6403722B1 (en) 2000-10-03 2002-06-11 The University Of Akron Dynamically vulcanized elastomeric blends including hydrogenated acrylonitrile-butadiene copolymers
US7037982B2 (en) 2001-01-17 2006-05-02 Bayer Aktiengesellschaft Rubber mixtures for roll coverings
US20030181604A1 (en) * 2002-01-23 2003-09-25 Roland Parg Nitrile rubber mixtures with a low tendency towards mold contamination
US6929769B2 (en) 2002-01-23 2005-08-16 Bayer Aktiengesellschaft Nitrile rubber mixtures with a low tendency towards mold contamination
US20040018312A1 (en) * 2002-07-25 2004-01-29 Lord Corporation Ambient cured coatings and coated rubber products therefrom
US6844412B2 (en) 2002-07-25 2005-01-18 Lord Corporation Ambient cured coatings and coated rubber products therefrom
US7737225B1 (en) 2005-02-18 2010-06-15 The United States Of America As Represented By The Secretary Of The Army High performance elastomeric compound
US20090011163A1 (en) * 2006-03-09 2009-01-08 Manoj Ajbani Compatibalized Blends of Polyphenylene Sulfide and Thermoplastic Vulcanizate
US20090061134A1 (en) * 2006-03-09 2009-03-05 Manoj Ajbani Flexible, hydrocarbon-resistant polyarylenesulfide compounds and articles
US7981981B2 (en) 2006-03-09 2011-07-19 Ticona Llc Flexible, hydrocarbon-resistant polyarylenesulfide compounds and articles
US8877306B2 (en) 2006-03-09 2014-11-04 Manoj Ajbani Compatibalized blends of polyphenylene sulfide and thermoplastic vulcanizate
US9494262B2 (en) 2012-04-13 2016-11-15 Ticona Llc Automotive fuel lines including a polyarylene sulfide
US9494260B2 (en) 2012-04-13 2016-11-15 Ticona Llc Dynamically vulcanized polyarylene sulfide composition
US9493646B2 (en) 2012-04-13 2016-11-15 Ticona Llc Blow molded thermoplastic composition
US9182056B2 (en) 2012-04-13 2015-11-10 Ticona Llc Pipe section having polyarylene sulfide composition barrier layer
US10563062B2 (en) 2012-04-13 2020-02-18 Avx Corporation Polyarylene sulfide for oil and gas flowlines
US9758674B2 (en) 2012-04-13 2017-09-12 Ticona Llc Polyarylene sulfide for oil and gas flowlines
US10501626B2 (en) 2012-04-13 2019-12-10 Ticona Llc Dynamically vulcanized polyarylene sulfide composition
US9765219B2 (en) 2012-04-13 2017-09-19 Ticona Llc Polyarylene sulfide components for heavy duty trucks
US10358556B2 (en) 2012-04-13 2019-07-23 Ticona Llc Blow molded thermoplastic composition
US10359129B2 (en) 2012-04-13 2019-07-23 Ticona Llc Automotive fuel lines including a polyarylene sulfide
US9757892B2 (en) 2013-08-27 2017-09-12 Ticona Llc Thermoplastic composition with low hydrocarbon uptake
US9718225B2 (en) 2013-08-27 2017-08-01 Ticona Llc Heat resistant toughened thermoplastic composition for injection molding
US10494467B2 (en) 2013-10-30 2019-12-03 Arlanxeo Deutschland Gmbh Copolymer rubber containing nitrile groups
US10544234B2 (en) 2013-10-30 2020-01-28 Arlanxeo Deutschland Gmbh Functionalized copolymer rubber containing nitrile groups
US12104058B2 (en) 2014-12-11 2024-10-01 Ticona Llc Stabilized flexible thermoplastic composition and products formed therefrom
US11046799B2 (en) 2016-01-25 2021-06-29 Arlanxeo Deutschland Gmbh Hydrogenated nitrile-butadiene-PEG-acrylate co-polymers
US11286325B2 (en) 2017-12-21 2022-03-29 Arlanxeo Deutschland Gmbh Nitrile-diene-carboxylic acid ester copolymers
US11827726B2 (en) 2018-12-17 2023-11-28 Arlanxeo Deutschland Gmbh Process for producing PEG acrylate-HNBR copolymer
WO2022064031A1 (en) * 2020-09-28 2022-03-31 Arlanxeo Deutschland Gmbh Partially hydrogenated diene polymers

Also Published As

Publication number Publication date
DE3046251C2 (de) 1985-08-08
JPS5682803A (en) 1981-07-06
JPS6261045B2 (enrdf_load_stackoverflow) 1987-12-19
DE3046251A1 (de) 1981-09-17
CA1172799A (en) 1984-08-14

Similar Documents

Publication Publication Date Title
US4384081A (en) Process for production of hydrogenated conjugated diene polymers
CA1216397A (en) Process for hydrogenating conjugated diene polymers
US4337329A (en) Process for hydrogenation of conjugated diene polymers
US4510293A (en) Process for hydrogenating conjugated diene polymers
JPH02178305A (ja) ニトリル基含有水素化重合体の製造方法
US4954576A (en) Process for hydrogenating conjugated diene polymers
US2786047A (en) Process for removing nickel catalyst from hydrogenated polybutadiene
JP2941897B2 (ja) ニトリル基を有する不飽和ポリマー類の水素添加
US5128297A (en) Method for hydrogenating conjugated diene polymer
CN107722145B (zh) 一种氢化丁腈橡胶的制备方法
EP0200029B1 (de) Verfahren zur Hydrierung nitrilgruppenhaltiger ungesättigter Polymerer
EP3116916B1 (en) Process for the reduction of nitrile groups of hydrogenated nitrile rubber
JPS6335641B2 (enrdf_load_stackoverflow)
JPH0142283B2 (enrdf_load_stackoverflow)
US3036025A (en) Rubbery diene polymer composition containing an oxidized polymer of butadiene
US5169901A (en) Method for hydrogenating conjugated diene polymer
US2959619A (en) Process for oxygenating polymers of butadiene
JPS6058242B2 (ja) 水素化共役ジエン系重合体の製造方法
JPS6136002B2 (enrdf_load_stackoverflow)
JPH06298844A (ja) 共役ジエン系重合体の水素化触媒、その製法および水素化方法
JPH04253706A (ja) 水素化ニトリルゴムの製造方法
US4115636A (en) Modified and stabilized synthetic cis-1,4 polyisoprene and method for producing same
US2485136A (en) Bonding rubber to cellulosic fibers
CN1189494C (zh) 一种双环戊二烯加氢石油树脂的制备方法
CN118406305A (zh) 一种高操控的备胎胎面橡胶组合物及其制备方法和备胎

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M171); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M185); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12